BRPI0814785B1 - GLUCOCYAMINE-CONTAINING MOLDS RESISTANT TO ABRASION AND FREE-FLOW, METHODS FOR THEIR PRODUCTION AND USE OF GLYCOCYAMINE-MOLDING - Google Patents

Description

(54) Title: MOLDINGS CONTAINING GLYCOCYAMINE RESISTANT TO ABRASION AND FREE FLOW, METHODS FOR THEIR PRODUCTION Ε THE USE OF MOLDINGS WITH GLYCOCYAMINE (51) Int.CI .: A23K 20/142; A61K 31/195; A23K 40/10 (30) Unionist Priority: 7/21/2007 DE 10 2007 034 102.6 (73) Holder (s): ALZCHEM TROSTBERG GMBH (72) Inventor (s): STEPHAN WINKLER; ROLAND MÕLLER; SUSANNE ERL

ABRASION-RESISTANT GLYCOCYAMINE CONTAINING MOLDINGS

AND FREE FLOW, METHODS FOR THEIR PRODUCTION AND USE

OF MOLDINGS WITH GLYCOCYAMINE.

description

The present invention relates to molds containing abrasion-resistant and free-flowing glycocyanins, as well as methods for producing them.

Glycocyanine is an endogenous substance in the bodies of vertebrates including humans, which plays a central role in the creatine biosynthesis. Creatine can not only be taken in the diet, but also endogenously formed, in which, as an energy-rich phosphocreatine, it is an important energy reserve of muscles, in addition to adenosine triphosphate (ATP). In the resting state of the muscle, ATP can transfer a phosphate group to creatine, with phosphocreatine being formed15 that is then in direct equilibrium with ATP. During muscle operation it is critical to fill ATP materials as quickly as possible. In the first few seconds of maximum muscle loading, phosphocreatine is available. It can transfer a phosphate group to adenosine diphosphate in a very rapid reaction via the enzyme chi20 nase and thereby reform ATP. This is also called the Lohmann reaction.

The beneficial effects of supplementation with creatine monohydrate have been known in humans for many years, especially in the field of sports nutrition, but also in the medical field.

The beneficial effects of dietary supplementation have also been on animals and creatine monohydrate has therefore been recommended for use as a food additive and as meat and bone meal substitute in animal nutrition. Since the ban on animal protein in feeds since 2000 in the United States, many diets for animal breeding and fat have been switched to purely vegetarian diets, with fishmeal also being substantially avoided, which is not included in the ban. . The switch to purely vegetarian diets led to 870170085836, of 11/8/2017, p. 9/22 caused losses in performance and, even after seven years, purely vegetarian diets are inferior to those containing animal proteins. One reason for this inferiority is the lack of creatine. Previous studies have clearly shown that creatine monohydrate added to food can improve growth performance when purely vegetarian diets are fed [Wallimann, T .; Pfirter, H.P .: Use of Creatine as a Feed Additive. EP1051914],

In addition to the undoubtedly beneficial effects, creatine monohydrate also has some disadvantages. The stability of this compound in aqueous solutions is highly restricted and creatine monohydrate, after oral administration, has only a low bioavailability. In addition, creatine monohydrate is a very costly substance and performance improvements in the field of animal growth are virtually offset by costs. Very recently, therefore, glycocyanine has also been used as a dietary supplement and food that, compared to creatine, in aqueous solution, has surprising stability and is significantly more bio-available [Gastner, T .; Krimmer, H.-P .: Guanidinoacetic acid used as an animal food additive. EP1758463]. Glycocyanine is converted very efficiently and quickly to creatine in the body. Therefore, glycocyanine can be administered in significantly lower amounts than creatine for the same effect.

In the literature, a multiplicity of synthetic methods have been described for the production of glycocyanine. In 1861, Strecker successfully synthesized glycocyanine from glycine and cyanamide for the first time [Strecker, M .; Jahresber. Fortschr. Chem. Verw., (1861), 530].

Similarly, Fromm in 1925 described the reaction of glycine hydrochloride with sodium cyanamide and hydrochloric acid to give glycocyanine hydrochloride [Fromm, E .; Justus Liebigs Ann. Chem., 442, (1925), 130-149],

Cyanamide was also used for the production of glycocyanine by Vassel in two patents. It was reacted with glycine, in which the pH was adjusted to 9.4 using sodium hydroxide [Vassel, B .; US2654779],

In addition, Vassel proposed the use of chloroacetic acid and ammonia. In this case, glycine hydrochloride was first formed. The resulting solution was subsequently adjusted to pH> 9 using sodium hydroxide solution and subsequently reacted with cyanamide [Vassel, B .; US2620354].

In 1903, the production of glycocyanine was described by Wheeler and Merriam by reaction of glycine with S-methyl isothiourea iodide in basic aqueous solution. In this case, potassium hydroxide was used as the base [Wheeler, H.I .; Merriam, H.F .; Am. Chem. Journal, 29, (1903), 478-492.]. A very similar procedure was described by Fischl in 1934, in which the base used was an excess of ammonia [Fischl, S .; (1931), US1967400].

In known methods, glycocyanine generally occurs as a finely crystalline to slightly yellowish white powder that has a considerable fraction of powder (particles <63 pm). The average grain diameter can vary within wide ranges and is generally between 25 and 150 pm. The glycocyanine obtained from the known synthesis has a powder fraction of more than 50% by weight and a free-flowing property of classification 6 and, therefore, it cannot be used for industrial food production.

The free flow property of powders, granules and extrudates can be determined, for example, via the flow behavior via test funnels having different discharge diameters (Feed Tech 9.10 / 2005, pages 23-26; see also the example section of the present invention). The free flow property in this case is rated from 1 for very good flow behavior to 6 for very poor flow behavior. For the production of industrial feeds, the solids used must reach at least a rating of 3.

For the abrasion resistance of feed and extruded granules, a non-uniform test protocol has been established so far. One method that has proven to be reproducible and meaningful in practice is abrasion (particles <63 pm) in an air jet screen over a defined period at a defined atmospheric pressure. In particular, measuring the difference in abrasion after 3 and 15 minutes at subatmospheric pressure of

7200 pascals have been established. In good granules this value is below

5% by weight. The method will be described in more detail in the example section.

The aim of the present invention was, therefore, to provide free-flowing, abrasion-resistant and therefore low-dust products that are suitable, in particular, for incorporation into foods, and also methods for producing them.

This objective is achieved according to the invention by providing molds containing free-flowing, abrasion-resistant glycocyamine having a mass density between 350 and 850 kg / m ³ , a grain size spectrum from 32 to 2750 pm and a content of glycocyanine from 55 to 99.9% by weight, based on the total weight.

It was found that with the provision of molds containing glycocyanine according to the invention, the objective was fully met, namely, providing free flow, abrasion resistance and, therefore, low-dust products for the food industry that are distinguished by good handling quality.

According to a preferred embodiment, these are granules and extrudates having a mass density between 400 and 800 kg / m ³ and, in particular, between 450 and 750 kg / m ³ . In addition, it is preferably considered that the grain size spectrum of the claimed moldings is between 32 and 1000 pm, and preferably less than 10% by weight of the particles is less than 100 pm and less than 10% by weight of the particles are above 850 pm. The moldings have a glycocyanine content of preferably 85 to 99% by weight, in particular 95 to 98.5% by weight.

In a preferred embodiment, the moldings contain organic or inorganic binders in amounts of 0.05 to 15% by weight, preferably 0.1 to 1.5% by weight, which are suitable for use in the products according to the invention as additives feed. Preferably, the binders used for the production of moldings are by-products or starting substances from the glycocyanine production process, such as glycine or glycocyanine salts, and thus they do not have to be separated in advance to purify the product. This proves to be particularly advantageous if small amounts of these substances still adhere in the dissolved form to the glycocyanine used, in which this can also be the glycocyanine itself dissolved in water.

Especially suitable is also the addition of other binders such as, for example, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxypropylmethylcellulose, hydroxymethylcellulose, microcrystalline cellulose, ethylmethylcellulose and other cellulose derivatives, starch, hydroxypropyl starch , pregelatinized or modified starch, sugar, sugar syrup, dextrin, gelatin, propyl vinyl alcohol, polyvinyl pyrrolidone, xanthan, glycocyanine salts, gum arabic, sodium chloride, sodium carbonate, sodium hydrogen carbonate and glycerol, and also mixtures thereof.

In order to improve the free flow property of the moldings, it may be advantageous that said moldings contain a flow intensifier, in particular a hydrophilic and / or hydrophobic silicic acid and / or additives based on silicate and / or fatty acids and / or salts thereof. , such as stearic acid or palmitic acid, and also sodium, potassium, and calcium salts thereof. Flow intensifiers and binders are added to glycocyanine in dry form, as a suspension, or solution, before molding, in which amounts of 0.01 to 5% by weight have proven to be adequate.

The present invention further provides that molds containing glycocyanine can optionally contain up to 40% by weight, in particular 1 to 10% by weight, of another nutritionally active substance from the group carbohydrates, fats, amino acids, proteins, vitamins, minerals, trace elements, and also derivatives thereof and mixtures thereof. Those that are preferred are considered to be, in particular, the essential amino acids lysine, threonine, methionine and tryptophan, and, in addition, vitamin A, vitamin D3, vitamin E, nicotinic acid, nicotinamide, β-carotene, fish meal and casein .

The glycocyanine-containing moldings according to the invention should preferably have a free-flowing property of classification 3, particularly preferably of classification 2 or 1, and also an abrasion resistance of less than 12% by weight, preferably less than 10% by weight, and, particularly preferably, less than 4% weight.

The invention also relates to a method for producing molds containing glycocyanine, characterized in that said molds are obtained by forming, in particular, mixed granulation or mold extrusion of a composition of glycocyanine and water and subsequent drying. The methods according to the invention can be carried out either continuously or as batch processes.

Extruders have been shown to be particularly suitable for forming, in particular single screw extruders, twin screw extruders, matrix ring presses and crushers. The solid used in this case is forced through an extrusion die generally at pressures up to 8 MPa (80 bars) and temperatures from 20 to 120 ° C. The size of the extrudate can either be adjusted by mechanical division, or the decomposition of the extrudates occurs with proper selection of process parameters. By this means, extruded between 32 and 2750 pm, in particular between 32 and 1000 p, can be generated.

In addition, granulators have been shown to be particularly suitable for forming, in particular intensive mixers, vertical granulators, spray granulators, layer ring granulators and coulter mixers. The solid used is exposed in this case to high shear forces in which, depending on the type, size and capacity of the granulator, speeds of 300 to 2500 revolutions per minute have proven to be adequate. Granulation can be carried out at temperatures between 20 and 120 ° C, in which the described method distributes granules between 32 and 2750 pm, in particular between 32 and 1000 pm.

Advantageously, the glycocyanine used for molding production is produced from glycine and cyanamide in an aqueous solvent, in particular water, with the addition of a base. Such methods are described, for example, in US 2,654,779 and US 2,620,354. In a preferred embodiment, water-wetted glycocyanine from the production process is used for granulation and extrusion, to which dissolved glycocyanine and / or starting materials or by-products from the production process still adhere. A residual humidity of 15 to 25% by weight of the material used has proved to be particularly advantageous in this case. In addition, mixtures used for forming can contain between 40 and 93% by weight of glycocyanine, between 7 and 60% by weight of water, between 0 and 15% by weight of binder, and also 0 to 40% by weight another nutritionally active substance.

It has been shown to be particularly advantageous not only for granulation but also for extrusion if the glycocyanine used has an average grain size diameter of <95 pm, preferably <25 pm, and in particular <15 pm.

In addition, amorphous glycocyanine, in particular, has been shown to be particularly suitable. For the invention, therefore, it is considered to be preferred that more than 40%, preferably more than 90% of the material used is in amorphous form. Particularly amorphous glycocyanine suitable for granulation can be generated, first by adjusting the appropriate process parameters in the production process that are known to those skilled in the art, and also by grinding crystalline material.

In order to obtain stable or extruded dry granules, the moldings are dried. In this case, especially movable bed dryers and fluidized bed dryers have proven to be particularly suitable in order to avoid mechanical destruction of molds that are still wet. Preferably, temperatures between 50 and 130 ° C and, optionally, vacuum, are used.

The powder content of the resulting and extruded granules is less than 5% by weight, preferably less than 2% by weight, as measured by the method of Dr. Groschopp.

Due to the very good abrasion resistance and free flow property, molds containing glycocyanine according to the invention are suitable as a feed additive.

The examples hereinafter are intended to illustrate the present invention in more detail.

Examples

1. Methods for determining abrasion resistance and free flow property

1.1 Abrasion resistance

The test medium consists of

- air jet screen

- 63 pm analytical sieve

- analytical balance (accuracy 0.01 g)

- industrial vacuum cleaner

- weighing plate g of the granules or extrudates to be determined are weighed and sieved for 3 min at atmospheric pressure of 7200 pascals in the air jet screen and subsequently re-weighed. The difference (= AW1) is equal to the abrasion resistance after 3 min. Subsequently, this operation is repeated with the same sample and in the same settings for 12 min sieving time and the sample re-weighed. The difference in the original weight (= AW2) is equal to the abrasion resistance after 15 min.

R _x = [(EW - AW _x ) x100) / EW]

R = Abrasion resistance [%]

AW = Weight after sieving [g]

EW = Initial weight [g]

The difference between the values at 3 min and 15 min is a measure of abrasion resistance. The higher this value, the more abrasion the material is generated.

1.2 Free-flowing property

The test medium consists of five test funnels having the same diameter and inclination angle, but having different discharge diameters (2.5 mm; 5 mm; 8 mm; 12 mm and 18 mm). The solid to be determined is loaded for this purpose in the test funnel, with the discharge being closed from the bottom so that no material can move during loading. In the next step, the discharge is opened completely, without shaking the test funnel, so that the complete discharge through the section is unimpeded. The evaluation parameter is the diameter in which the solid flows spontaneously and without external action. In this test the following applies:

• The solid flows through the 2.5 mm discharge: classification • The solid flows through the 5 mm discharge: classification 2 • The solid flows through the 8 mm discharge: classification 3 • The solid flows through the 12 mm discharge : classification • The solid flows through the 18 mm flush: classification • The solid does not flow through the 18 mm flush: classification 6.

2. Production of granules and extrudates

2.1 In a 75 liter intensive mixer (from Eirich), 34 kg of glycocyanine (KGA x value 50 (average grain size diameter) = 13.6 pm) having a water content of 20.8% were loaded at temperature room and homogenized for 1 min. Subsequently, 269 g of starch are added under low agitation. Then, the contents of the mixer are stirred at 1500 rpm, in the course of which the temperature has increased to approximately 50 ° C. After 5 min of granulation time, granules of the desired grain size range were obtained. The resulting glycocyanine granules were dried in a fluid bed dryer at a product temperature of 80 ° C and subsequently the coarse fraction above 1.00 mm was sieved.

2.2 In a vertical granulator, 35 kg of glycocyanine (KGA x value 50 = 23.2 pm) having a residual humidity of 13% were loaded at room temperature and homogenized for 1 min. Subsequently, 305 g of starch and 2.60 kg of water were added with low agitation. Then, the contents of the mixer were stirred at 2000 rpm, in the course of which the temperature increased. After 8 min of granulation time, the granules in the desired grain size range were obtained. The granules were dried in the vacuum drying cabinet at 80 ° C and

5000Pa (50 mbars).

2.3 4.3 kg of glycocyanine (KGA x value of 50 = 12.6 pm) having a residual humidity of 20.7% were loaded into a mixer and 34 g of starch were mixed with slow stirring. Subsequently, the mixture was placed in a matrix ring extruder and forced through a matrix having holes of 0.7 mm. The resulting extrudate was dried in a fluid bed dryer at a product temperature of 50 ° C.

2.4 In a 75 liter intensive mixer (from Eirich), 34 kg of glycocyanine (KGA x value of 50 = 63.8 um) with a residual humidity of 9.4% were loaded at room temperature and homogenized for 1 min.

Subsequently, 308 g of starch and 3.57 kg of water were added with slow stirring. Then, the contents of the mixer were stirred at 1500 rpm, in the course of which the temperature increased to approximately 50 ° C. After 6 min of granulation time, an additional 0.94 kg of water was added and the mixture was again granulated for an additional 6 min. The resulting granules were dried in the vacuum drying cabinet at 80 ° C and 5000 Pa (50 mbars).

Table 1: Screening analysis, free flow property, resistance to abrasion and mass density of the resulting granules.

Example 2.1 Example 2.2 Example 2.3 Example 2.4 g <63 pm | 63-100 pm E 100-200 pm 2 φ 200-315 pm o- 315-500 pm ω 2 500-710 pm V) 710-850 pm ^< > 850 pm 1.3 2.8 7.8 17.2 47.5 19.0 3.3 1.2 4.4 0.4 10.8 9.5 14.5 30.5 21.5 8.4 1.4 0.8 0.6 0.8 2.3 89.8 3.6 0.7 8.6 12.6 30.1 22.3 24.7 1.6 0.0 0.0 Free-flowing property [classification] 2 2 3 3 Fraction <63 pm [%] 1.3 4.4 1.4 8.6 Mass density [g / l] 587 617 532 426 g AND S after 3 min V > after 15 minutes ω <0 xj difference between 3 and 15 min · «_ φ CO 1.3 4.4 3.1 7.9 14.8 6.9 1, -6 4.8 3.2 8.6 17.0 8.4

Claims (16)

1. Molding containing abrasion-resistant and free-flowing glycocyanine, characterized by the fact that it has a mass density between 350 and 850 kg / m ³ , a grain size spectrum of 32 to 5 1000 pm and a glycocyanine content of 55 to 99.9% by weight, based on the total weight, in which less than 10% by weight of the particles are below 100 pm, and less than 10% by weight of the particles. particles are above 850 pm. 2. Molding according to claim 1, characterized in that said molding contains organic or inorganic binders in amounts of 0.05 to 15% by weight, preferably 0.1 to 1.5% by weight. 3. Molding according to claim 1 or 2, characterized by the fact that methylcellulose, ethylcellulose, carboxymethylcellulose, car15 boxethylcellulose, carboxy-propylcellulose, hydroxypropylmethylcellulose, hydroxymethylcellulose, microcrystalline cellulose, ethylmethylcellulose and other cellulose derivatives, starch starch, native starch, pregelatinized or modified starch, sugar, sugar syrup, dextrin, gelatin, propyl vinyl alcohol, polyvinyl pyrrolidone, xanthan, glycine, glycocyanine salts, arabic gum, sodium chloride, sodium carbonate, hydrogen carbonate sodium, glycerol and, optionally, mixtures thereof, are used as binders. Molding according to any one of claims 1 to 3, characterized in that said molding has a glycocyanine content of 85 to 99% by weight, preferably 95 to 98.5% by weight. 5. Molding according to any one of claims 1 to 4, characterized in that said molding has a density 33 of mass between 400 and 800 kg / m ³ , preferably 450 to 750 kg / m ³ . 6. Molding according to any one of claims 1 to 5, characterized by the fact that said molding contains up to 40% in 30 weight of other nutritionally active substances in the group carbohydrates, fats, amino acids, proteins, vitamins, minerals, trace elements, and also derivatives thereof and mixtures thereof. Petition 870170085836, of 11/08/2017, p. 10/22 Molding according to any one of claims 1 to 6, characterized in that said molding has a free flow property of classification 3, preferably of classification 2 or 5 1. 8. Molding according to any one of claims 1 to 7, characterized in that said molding has an abrasion resistance of less than 12% by weight, preferably less than 10% by weight, and, particularly preferably , less than 4% by weight. 9. Molding according to any one of claims 1 to 8, characterized in that said molding contains, as a flow intensifier, a hydrophilic or hydrophobic silicic acid, or silicate-based additives, or fatty acids, or salts of themselves, or mixtures 15 of these flow intensifiers in amounts of 0.01 to 5% by weight. 10. Method for producing molds containing abrasion-resistant and free-flowing glycocyanins, as defined in any one of claims 1 to 9, characterized in that said moldings are obtained by mixed granulation of a composition of 20 glycocyanine and water, and subsequent drying of the resulting granules. 11. Method according to claim 10, characterized in that the intensive mixers, vertical granulators, spray granulators, ring-layer granulators and coulter mixers are used as granulators. 25 12. Method for producing molds containing abrasion resistant and free flowing molds, as defined in any of claims 1 to 9, characterized in that said moldings are obtained by mold extrusion of a composition of glycocyanine and water, and subsequent drying of the resulting extrudates. 30 13. Method according to claim 12, characterized by the fact that single screw extruders, twin screw extruders, ring mold presses and crushers are used as an extruder. Petition 870170085836, of 11/08/2017, p. 11/22 14. Method according to any one of claims 10 to 13, characterized by the fact that a water-moist glycocyanin separated from the production process, and having a residual moisture of 15 to 25% by weight, is used. 15. Method according to any one of claims 10 to 14, characterized in that a used mixture contains between 40 and 93% by weight of glycocyanine, between 7 and 60% by weight of water, between 0 and 15% by weight of binder, and 0 to 40% by weight of another nutritionally active substance. 16. Method according to any one of claims 10 to 15, characterized in that the glycocyanine used has an average grain size diameter of <95 pm, preferably <25 pm, and particularly preferably <15 pm . 17. Method according to any one of claims 10 15 to 16, characterized by the fact that more than 40% by weight of the glycocyanine used is in amorphous form. 18. Method according to any one of claims 10 to 17, characterized in that the resulting molds containing glycocyanine are dried, optionally under vacuum, at temperatures of 50 to 20 130 ° C. 19. Method according to any one of claims 10 to 18, characterized in that the glycocyanine used was produced from glycine and cyanamide in an aqueous solvent with the addition of a base. 20. Use of molds containing abrasion-resistant and free-flowing glycocyanine, as defined in any of claims 1 to 9, characterized in that said moldings are used as a feed additive. Petition 870170085836, of 11/08/2017, p. 12/22